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Improvement of Essential Oil Steam Distillation by Microwave Pretreatment

Article  in  Industrial & Engineering Chemistry Research · April 2011

DOI: 10.1021/Ie102218g

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 ARTICLE

pubs.acs.org/IECR

Improvement of Essential Oil Steam Distillation by Microwave

Pretreatment
A. Navarrete, S. Wallraf, R. B. Mato,* and M. J. Cocero
Department of Chemical Engineering and Environmental Technology, School of Industrial Engineering (Dr. Mergelina), University of
Valladolid, 47011 Valladolid, Spain

ABSTRACT: Microwave irradiation is proposed as a pretreatment method to accelerate the conventional steam distillation of
rosemary essential oil. Microwave extraction methods are based on the capacity of radiation to break the oil-containing glands,
allowing faster extraction rates. An analytical method is developed to quantify the fraction of essential oil inside and outside
trichomes. This method is used to evaluate the effect of microwaves on the fraction of oil released outside of trichome glands. Steam
distillation rates are measured after using different microwave pretreatment energies, and the influence of liquid moisture released
from plant cells is also analyzed.

1. INTRODUCTION steam.10,11 This mechanism reveals the advantage of using

Essential oils are the ethereal fraction obtained by physical
means from a plant. Essential oils have been extracted from over
3000 plants, 200
300 of which are commonly traded on world
markets.1 Main uses are in the perfume and flavor industries,
although they are also used in the food and pharmaceutical
industries as preservatives (mainly antioxidants) and flavors.
Also, compounds in essential oils with a phenolic structure have
been identified to be active against micro-organisms.2
The industrial extraction of essential oils is usually carried out
via steam distillation. Other methods of extraction include
hydrodistillation, solvent extraction, or supercritical solvent
extraction. Recently, several extraction techniques have also been
published using microwave energy.3 The latter are mainly
intended for analytical purposes; however, the reported reduc-
tion in energy requirements and operating time4
6 makes them
suitable for industrial processing. Some preliminary studies6,7
indicate that the cost of microwave extraction could be compe-
titive with traditional steam distillation. However, two character-
istics diminish this advantage of reduced energy and shorter
operating time: (1) high investment cost of the continuous
microwave oven, which must operate separating vapor and
exhausted plant, and (2) high operating cost of electricity, in
comparison with the much less-expensive cost of fuels used to
operate steam distillation. Most of the operating cost in both
steam distillation and microwave extraction corresponds to the
energy required to generate the mass of steam necessary to
extract all the essential oil present in the aromatic plant.
Essential oil is mostly present in the plant in special glands
named trichomes. During steam distillation, as steam flows over
the oil-containing glands, the trichomes slowly release their
content, because of high temperature, and, finally, become
deflated when they release all their essential oil content.8,9
However, when microwave energy instead of steam is used, the
interaction of the electromagnetic field with the polysaccharide
molecules and moisture present in trichome walls causes wall
breakage. So, essential oil is quickly released outward from
trichomes and is ready to be evaporated by the surrounding
microwaves for essential oil extraction since, from the initial
period of the process, oil may be evaporated by steam in an oil:
steam ratio close to vapor
liquid equilibrium. In contrast, in
pure steam distillation, oil is only released slowly from the inside
of the trichomes.
Based on these facts, a new coupled process may be suggested,
which takes advantage of both methods of extraction. First, a
short microwave pretreatment is applied to the plant in order to
break all trichome walls and release the entire oil content on the
surface of the plant. Second, inexpensive conventional steam
distillation is performed in the pretreated plant.
This process depends on the performance of the first stage. If
trichome wall breakage is fast, and no steam is generated from
plant moisture at this stage, then energy consumption will be low,
and, moreover, no vapor recovery device will be required in the
continuous microwave oven. Next, conventional steam distilla-
tion will extract oil at a faster rate, reducing energy demand and
operating time, and, consequently, equipment size.
To the knowledge of the authors, no method has been
proposed to date to measure and evaluate the extent of trichomes
breakage. The aim of this paper is to determine how trichome
wall breakage evolves under microwave irradiation, and how their
main operating variables affect the process.
Microscopic methods (optical and electronic) have been
previously used to verify the status of trichomes before and after
oil extraction, both in steam distillation and in microwave
extraction.6 However, microscopy was discarded as a convenient
measuring technique, because of the difficulty to quantify the
ratio of exploited to intact glands, from a representative sample.
Instead of the number of trichomes, the concepts of “oil
trapped inside trichomes” and “oil released out of trichomes”
were chosen to quantify the effect of microwave pretreatment.
Received: November 2, 2010
Accepted: March 1, 2011
Revised: January 16, 2011
Published: March 15, 2011

r 2011 American Chemical Society 4667 dx.doi.org/10.1021/ie102218g | Ind. Eng. Chem. Res. 2011, 50, 4667–4671
Industrial & Engineering Chemistry Research ARTICLE

The released oil fraction is defined as

mr
Y ¼ ð1Þ
mr þ mt
where mr is the mass of oil released out of trichomes, accessible to
be evaporated by steam, and mt is the mass of oil that remains
trapped inside of trichomes.
The essential oil content in aromatic plants is usually deter-
mined by the standard analytical method, using a Clevenger
distiller.12 However, this method extracts oil by distillation and
does not allow one to distinguish between released and trapped
oil fractions.
Since both oil fractions have the same chemical composition,
an alternative method has been developed to quantify their
values. This method uses solvent extraction and is based on Figure 1. Experimental setup. (Legend: [1] microwave oven, [2] glass
the differences in extraction kinetics for both fractions. flask, [3] rotary fitting, and [4] condenser.)
Once trichome breakage kinetics are known, the influence of
the released oil fraction of the plant material on steam distillation
evolution is determined, performing conventional steam distilla-
tion with a plant pretreated with microwave radiation.

2. EXPERIMENTAL PROCEDURES
2.1. Plant Material. For all experiments, rosemary
(Rosmarinus officinalis L.) was selected, because it is a local
representative of aromatic plants grown in this region. Rosemary
was collected in September 2009 in Pe~ nafiel (Valladolid, Spain).
Plants were stored at 4 °C until needed for the extractions. The
maximum storage time before use was one month. At the
moment of being used, entire leaves were carefully separated
from the stems and used in the experiments without crushing.
2.2. Analytical Techniques. 2.2.1. Moisture Measurement.
Moisture content was determined using the gravimetric method
as the ratio of water to total mass. A sample of ∼0.10 kg was
weighed before and after 24 h of oven drying at 105 °C. Moisture
content was in the range of 49.2%
62.5%.
2.2.2. GC-MS Analysis. Oil composition was obtained using gas
chromatography coupled to mass spectrometry (GC-MS). GC-
MS analyses were carried out with an Agilent 6890/5973
(Agilent Technologies, Palo Alto, CA, USA). The column used
was manufactured by Hewlett
Packard, Model HP-5MS; carrier
gas, He; flow, 0.7 mL/min; mode, split; split gas, He; split ratio,
200:1; injection temperature, 250 °C; and injection volume, 1
μL. Column temperature started at 70 °C, hold for 1 min, and
then increased at 3 °C/min until 160 °C.
To measure the evolution of oil components over time, an
internal standard (linalyl acetate 0.5 wt %) was added to the
solvent (n-hexane in steam distillation and ethanol in solvent
extraction) to improve analytical accuracy. The relative areas
between a given component and the internal standard were
correlated versus their relative masses in the sample. The exact
amount of the extracted compound of interest was determined
from the peaks ratio and the known composition of internal
standard in the solvent. The measured components were chosen
to represent rosemary essential oil, in terms of composition and
volatility: R-pinene (CAS No. 80-56-8), eucalyptol (CAS No.
470-82-6), and camphor (CAS No. 76-22-2).8
2.3. Trichome Breakage. 2.3.1. Microwave Pretreatment.
The plant material was exposed to microwave radiation before
steam distillation experiments, in order to promote breakage of
the trichome wall. The experimental setup is shown in Figure 1.
Exposition of rosemary leaves (100 g approx.) to microwave
Figure 2. Experimental conditions used in microwave pretreatment.
energy was carried out in a 500-mL glass flask introduced in a
modified microwave oven (Panasonic Model NN-GD 566 M).
During microwave heating, the sample rotates inside of the
cavity. This setup allowed the samples to move through the
uneven electromagnetic field pattern formed inside the oven,
allowing for a somewhat more uniform energy absorption in the
material plant. This setup configuration significantly improved
the reproducibility of experimental results. In order to prevent
the loss of essential oil, the oven was adapted to condense the
possible evaporation of volatile material leaving the plant con-
tainer. However, condensation out of the flask was not observed
in any of the experiments, because of the low energy values used
in the pretreatment.
The experimental conditions used in microwave pretreatment
are shown in Figure 2. Different combinations of oven power and
operation time were selected to irradiate energies up to 1 kJ/g, on
a dry-plant basis.
After microwave pretreatment, the plant container was im-
mediately taken out of the oven and subjected to one of the two
following procedures: (1) steam distillation, to determine ex-
traction kinetics, or (2) solvent extraction, to evaluate the
trapped and released oil fractions, as explained in the following
section.
2.3.2. Solvent Extraction. The aim of solvent extraction
experiments was to determine the fractions of “oil trapped inside
trichomes” and “oil released out of trichomes”, after microwave
pretreatment. The quantification method exploits differences in
the solvent extraction kinetics for both fractions.

4668 dx.doi.org/10.1021/ie102218g |Ind. Eng. Chem. Res. 2011, 50, 4667–4671

Industrial & Engineering Chemistry Research
Figure 3. Time evolution of solvent extraction of R-pinene at tempera-
tures of 2.6, 13.9, and 24.8 °C.
Solvent selection must be carefully done, since some solvents
(e.g., n-hexane) cause trichome wall damage, releasing part of the
oil from the glands.13 Ethanol, however, has proven to be a more
friendly solvent to trichome walls, allowing different extraction
kinetics to released and trapped oil.13,14 For this reason, ethanol
was chosen to perform this part of the work. The use of
an impeller to improve oil extraction was discarded, to avoid
damage to the trichomes. Instead, the use of a rotavapor (Buchi
RE 111) was chosen, to provide gentle stirring to the plant
material, along with the solvent, without altering the integrity of
the trichomes.
Finally, an experimental screening of extraction time and
temperature conditions was performed to determine the optimal
conditions needed to clearly separate the fractions of released
and trapped oil. A flask with 50 g of fresh rosemary leaves was
connected to the rotavapor and deposited in a bath of glycol at a
preset temperature, allowing rotation at 5.5 rpm. Simultaneously,
a flask with a solution of linalyl acetate (0.5% w/w) in ethanol was
also thermostatted in the bath. Once thermal equilibrium was
reached, solvent extraction was started by adding 200 mL of
ethanol solution to the leaves. To measure solvent extraction
evolution, several samples of 1.5 mL of solvent were taken at
different extraction times and then filtered (0.2 μL nylon filter,
Millex-GN) into amber sampling flasks.
Figure 3 shows time evolution of the extracted mass of R-
pinene, at different temperatures. In all cases, there was a fast
extraction stage in the initial 30 min, where it is assumed that the
entire fraction of released oil was extracted by the solvent. At low
temperature (2.6 °C), no oil trapped inside trichomes was
extracted by the solvent within the next 5 h. At higher tempera-
ture, the trapped oil extraction rate from inside trichomes was
increased, overlapping with the released oil extraction stage at
24.8 °C. From these results, the measurement procedure was
established as follows: first, the released oil fraction was extracted
at 3 °C for 60 min, and, after taking a sample of solvent, the bath
temperature was increased to 40 °C for 180 min. A new sample
was taken to determine the remaining oil fraction that was
initially trapped inside trichomes.
2.3.3. Steam Distillation. Steam distillation experiments were
performed with fresh and microwave-pretreated plant material,
in order to evaluate the influence of the released oil fraction on
distillation kinetics.3,8
4669
ARTICLE
Figure 4. Released oil fraction as a function of microwave pretreatment
energy, calculated from solvent extraction with ethanol at 3 °C for
60 min.
Fresh plant (l00 g approx.) was placed in a flask for microwave
pretreatment. Next, the flask was connected to the steam
distillation unit. The steam was produced in a separate boiler
by electrical heating (380 w) and passed through the fresh plant.
The vapor leaving the plant flask was condensed, and a solution
of linalyl acetate (0.5% w/w) in hexane was used to collect the
distilled oil. This method reduces oil loss over condenser walls.
During the distillation process, seven fractions, corresponding to
consecutive distillation periods, were taken to examine the
evolution of oil extraction. The samples were deposited in amber
flasks and kept at 4 °C until GC/MS analysis.
3. RESULTS AND DISCUSSION
3.1.1. Solvent Extraction. Solvent extraction experiments to
determine the fraction of oil released out of trichomes were
performed with fresh and microwave-pretreated plant material,
according to procedures described in section 2.3.2, using ethanol
at 3 °C for 60 min. Figure 4 shows time evolution of the extracted
mass of main oil components in solvent extraction, after using
different microwave energies in plant material pretreatment.
Figure 4 illustrates how an increasing amount of irradiated
energy significantly increased the fraction of released oil caused
by the breakage of trichomes. The three components chosen to
characterize the oil show a very similar behavior, represented by
the average line. Differences in release of three components at
intermediate power input may be explained by the steep slope of
the curve at these energy values. Therefore, the oil composition
was not modified during the extraction process, indicating that
there was no effect of the fractionation of oil at the microwave
pretreatment stage. The use of irradiation energies below 0.30
kJ/gdry-plant had little effect on the integrity of trichomes. How-
ever, in the range of 0.30
0.60 kJ/gdry-plant, almost all trichomes
on the plant became broken, and their trapped oil was released to
be easily accessible.
3.1.2. Steam Distillation. Steam distillation experiments were
carried out to quantify the influence of the microwave pretreat-
ment on distillation kinetics, since the rate of extraction of
essential oil during steam distillation was expected to be related
to the released oil fraction. Experimental results, for the case of R-
pinene, are shown in Figure 5. The condensed mass of R-pinene
is represented as a function of the condensed water mass, in order
to compare the obtained saturation level of the vapor phase using
dx.doi.org/10.1021/ie102218g |Ind. Eng. Chem. Res. 2011, 50, 4667–4671
Industrial & Engineering Chemistry Research
Figure 5. Time evolution of the extracted mass of R-pinene obtained by
steam distillation, after microwave pretreatment with 0.00, 0.10, 0.45,
0.59, and 0.90 kJ/gdry-plant.
Figure 6. Yield of R-pinene, eucalyptol, and camphor (g/gdry-plant)
obtained by steam distillation, as a function of pre-irradiated microwave
energy.
different preirradiated energy levels. A similar behavior was
observed with eucalyptol and camphor and, therefore, is assumed
to be representative of the total oil content.
As expected, experiments with 0.00 and 0.10 kJ/gdry-plant (both
below the 0.30 kJ/gdry-plant threshold) showed similar behavior.
When the irradiated energy is increased up to 0.45 kJ/gdry-plant,
the rate of extraction increased greatly and a much larger quantity
of essential oil was obtained with less steam. However, the use of
further increases in the preirradiated energy (0.59 kJ/gdry-plant)
progressively reduced the rate of extraction, returning to non-
irradiated behavior when the maximum energy value (0.90 kJ/
gdry-plant) was used. This behavior is clearly seen in Figure 6,
where the steam-distillation yield of the three analyzed compo-
nents is presented as a function of the preirradiated microwave
energy. The effect of the pretreatment is not clear below 0.30 kJ/
gdry-plant. A maximum value is reached at 0.45 kJ/gdry-plant, and the
effect decreases again when larger energies are used.
In the microwave pretreatment process, there was no con-
densation of water or oil in the condenser located out of the oven
to prevent the possible evaporation of volatile material leaving
the plant container. Therefore, this reason was discarded as a
possible explanation for the decrease in yield at higher microwave
power input (shown in Figure 6).
4670
ARTICLE
Figure 7. Time evolution of the extracted mass of eucalyptol, obtained
by steam distillation after microwave pretreatment with 0.54 kJ/gdry-plant.
Comparison between experiments with and without intermediate plant
drying.
This behavior was attributed to the liquid moisture released
from plant cells when they are irradiated, as it happens with
essential oil. In fact, in the Solvent Free Microwave Extraction
(SFME) process,4 this plant moisture is used to distill the
essential oil from the plant without a need for additional steam.
The effect of moisture on plant surface in the steam distillation
process has been previously described.15,16 Steam only con-
denses into water surfaces in immediate contact with oil, at the
oil/water interface, where latent heat is released to vaporize the
oil. Oil and water on the plant surface intermingle at the interface
by capillary action, under ideal conditions. This situation allows a
large contact perimeter and, therefore, fast extraction rates.
However, when the liquid moisture released by radiation is too
high, the excess of water may flood the herb surface and over-
whelm its absorptive capacity. This fact leads to the formation of
circular drops of oil on water, with a thin circular line of contact.
The area into which steam could usefully condense would be
insignificant and very little oil would vaporize.
Based on the previous argument, one experiment (0.54 kJ/
gdry-plant) was repeated but, between the microwave pretreatment
and the steam distillation operations, the leaves were dried in the
ambient environment for one day, to reduce the water content on
the plant surface. The rate extraction for this experiment,
corresponding to eucalyptol, is shown in Figure 7, in comparison
with the same experiment carried out without the intermediate
drying.
When the water content over the plant surface is reduced
before steam distillation, the rate of extraction is clearly increased
and the operation time is reduced. This behavior lays the
groundwork for a possible application of microwaves as pretreat-
ment previous to steam distillation extraction of essential oils.
4. CONCLUSIONS
Traditional steam distillation is a slow and high-energy-
demanding process. These two negative characteristics are a
consequence of the slow thermal release of essential oil from
inside trichome glands. This article studies the use of microwave
energy to promote the breakage of trichome walls and release the
essential oil to make it available to steam distillation. A novel
technique to measure the fraction of essential oil inside and
dx.doi.org/10.1021/ie102218g |Ind. Eng. Chem. Res. 2011, 50, 4667–4671
 Industrial & Engineering Chemistry Research ARTICLE

outside trichomes is described, based on differences on extrac-
tion rate kinetics with temperature, using ethanol as the solvent.
When fresh rosemary leaves are irradiated with microwave
energy, trichome breakage starts to be effective at 0.30 kJ/gdry-plant,
and it is completed at an energy input of 0.60 kJ/gdry-plant.
Steam distillation experiments confirm how low-energy irra-
diation pretreatment (up to 40 kJ/gdry-plant) improves the steam
distillation kinetics. However, when a higher energy is used to
promote complete breakage of trichomes, steam distillation
efficiency is reduced. As an effect of microwaves, the liquid
moisture released by plant cells covers the plant material,
reducing its absorptive capacity. The oil and water interface
diminishes and the distillation kinetics are decreased. When
pretreated material plant was dried in an ambient environment
after irradiation, the absorptive capacity of the plant surface was
recovered, and the steam distillation rates were clearly
improved again.
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Solvent free microwave extraction of Elletaria cardamomum L.: A
multivariate study of a new technique for the extraction of essential
oil. J. Food Eng. 2007, 79 (3), 1079–1086.
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Essent. Oil Rev. 1928, 23, 467–503.
(13) Chen, S. S.; Spiro, M. Kinetics of microwave extraction of
rosemary leaves in hexane, ethanol and a hexane þ ethanol mixture.
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Production, Analysis; D. Van Nostrand: New York, 1948.

’ AUTHOR INFORMATION
Corresponding Author
*Tel.: þ34 983 423 177. E-mail: rbmato@iq.uva.es.

’ ACKNOWLEDGMENT
The authors wish to thank the financial support of the
Agricultural Technology Institute of the Junta de Castilla y Leon
(ITACyL, project reference VA-12-C2-1), and the Junta de
Castilla y Leon (Project GR11-2008).

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